Resinous composition



Patented Jam 14,1941- Hans John, Appleton, Win, aslignor to Paper Patents Company, Neenah, Win, a corporation of-W No Drawing.

Application September 3. 193a,

Serial No. season 11 Claims. (o1. zoo-'42) The present invention relates to compositions of matter exhibiting properties found ,in synthetic resins and includes an improved process for ob- 'taining said compositions. The ingredient or 6 ingredients makingup the principal part or parts of the compositions of the present invention are obtained from dilute waste sulphite liquor, and preferably from the spent or wasteliquor as drained'from the pulp in the sulphite pulping in process. 1

In the sulphite process for the production of chemical wood pulp, the reagents used in the cooking liquor for the decomposition of the wood comprise ordinarily a water solution of sulphur 15 dioxide and, in addition, some alkaline earth or alkali metal or ammonium salt ofsulphur did!!- me usually in the form of bisulphite such as calcium bisulphite. The disposal of the waste liquor remaining'from-thisprocess after recovery of the 20 cellulose per se for use in the manufacture of paper has long been a major problem in the pa-,- per industry. Prior suggestions calling for the evaporation of the liquors and the disposal of the solid residue-have been found economically'im- 25 practical due to prohibitive cost.

The art has known for some time that spent liquors from the sulphite process contain various compositions including potential rwinous compositions, which have commercial .value. Suggestions by prior investigators for recovering the resinous compositions by concentration of the sulphite liquor have, as indicated above, been found commercially impractical. Other attempts by the art to separate the resinous compositions by chemical precipitation have also been rejected for the most part by the paper industry due primarily to high cost and the diillculty encountered in the separation of the precipitate from the liquor. As far as I have been able to ascertain, no one has heretofore suggested a practical method of obtaining resinouscompositions from sulphite liquor.

Therefore, one of the principal objects of the present invention is to provide a process for re- 45 covering resinous compositions from-sulphite'iiquors readily adaptable for commercial application.

Another object of the present invention is to provide novel compositions possessin properties 50 present insynthetic resins.

Other obJects will be apparent from the following detailed description.

I have discovered that resinous compositions may be recovered by a precipitation process fromcorrosive.

with the'sulphite liquor an amine and an aidehyde in the presence of a. strong acid. I have also discovered that the precipitates obtained by the above process are readily separable from the liquor, exhibit properties found in synthetic resins 5 and are adaptable for use in molding compositions'.

The processes of ,thepresent invention employ dilute spent or waste sulphite liquors having. a concentration of solids up to, approximately 45 ample, when using concentrated liquors the heat of reaction drives off-large amounts of volatile aldehyde, e. g. formaldehyde, and the precipitate which cakes in the concentrated liquors makes mixing very difficult and the preparation of uniform reaction products practically impossible. Also the precipitates obtained from concentrated liquors have been found in many cases to be incompletely resinifled, hygroscopic and highly In addition, molded products made from precipitates obtained from concentrated liquors have been foundto bepoor in strength, 5 brittle and easily fractured, to have a tendency to char and to have a poor surface due to gas pits.

Preferably the processes of the present invention utilize spent liquor as it comes from the sulphite digesters inwhich the liquor has a concentration of solids of about 10 to 15 percent. When using the dilute liquors of the present invention the loss of volatile aldehyde is prevented and the resulting products are uniform or homogeneous. The precipitates obtained from dilute liquors are substantially free from occluded water soluble materials and are free from the undesirable properties found to be present in-products obtained from concentrated liquors. In view of the above the term "dilute" liquor occurring throughout the present specification and claims is intended to cover spent or waste'sulphite liquors having a concentration of solids of 45 percent orless.

The following examples. will serve to illustrate the present invention: 45

will I To 1000 c. c. of dilute spent acid sulphite liquor preferably stirred by an agitator isadded'20-25' gramsof aniline. The resulting 'clearsolution go assumes a colorationthat can be. likened to that of choke cherry' Juice. About 25-35 grams .of commercial 40 percent formaldehyde solution "(formalinlare next added tothe agitated mixture followed the addition of'10-l5 c. c. 'of 1: 1 5

sulfuric acid, i. e. 1 volume of concentrated suliuric acid (sp. gr. 1.84) mixed with 1 volume of water. The temperature of the reaction mixture is preferably maintained at an elevated temperature of at least 50 C. which is suilicient to produce a heavy reddish-yellow precipitate in less than 1 minute after the addition of the final ingredient. The precipitate is readily separated by filtration and is washed with water in the usual manner. My investigations have shown theprecipitates obtained when the reaction mixture is maintained at 70-90 C. to have an astonishingly high rate of drainage, in fact so rapid that the rate is comparable to that of an aqueous suspension of sea sand, no suction being required during washing on the filter. Precipitation at ordinary or room temperatures requires about 2 minutes and the precipitates obtained filter at a slower rate than those obtained at temperatures of at least 50 C. In some cases precipitation under heat and pressure have been found desirable.

- EXAMPLE II To 1000 c. c. of a vigorously agitated dilute spent acid sulphite liquor solution about 25 grams of aniline are added, followed by the addition of 15 c. c. of 1:1 sulfuric acid and 15 grams of formalin. The mixture in which a yellowish precipitate is forming is stirred for about 15 minutes and then 25 grams of furfural are progressively added in small portions. Theaddition of thefurfural causes the precipitate to assume a dark red color and increase greatly in particle size. The precipitate obtained at ordinary temperatures in accordance with this example exhibits an astonishing rate of settling after agitation is discontinued. My investigations show that the precipitate when formed at high temperatures has a strong tendency, when agitation is stopped, to coalesce and form a coherent resinous substratum which is readily separable from the liquor. This precipitate should also be washed in the usual manner. The preferred materials for use in the present invention includeprimary aromatic amines such as aniline, toluidine, xylidine, phenylene diamine, toluylene diamine, benzidine, tolidine and naphthylamine, and aldehydes such as formaldehyde,

EXAMPLE Ill Formaldehyde reaction products (a) Dilute waste sulphite liquor l cubic centimeters 1000 Aniline grams 25 H2804 (1:1) cubic centimeters- Formalin grams 20.1

(b) Dilute waste sulphite liquor.

cubic centimeters" 1000 Aniline H2804. (1:1) cubic centimeters 22.5

Formalin grams 10.1

Dilute waste sulphite liquor l cubic centimeters Aniline grams H2804 (1:1) cubic centimeters Formalin grams Dilute waste sulphite liquor cubic centimeters o-Toluidine grams Formalin do H2804 (1:1) cubic centimeters Dilute waste sulphite liquor cubic centimeters" Para toluidine grams Formalin do.. H2804 (1:1) cubic centhneters Dilute waste sulphite liquor--- cubic centimeters Xylidine grams Formalin do Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimeters;

m-Phenylenediamine grams Formalin ..do Conc. HCl ..cubic centimeters Dilute waste sulphite liquor cubic centimeters Para phenylenediamine grams Formalin do- Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimeters 2, 4 toluylenediamine grams Formalin do Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimeters Benzidine "grams" Formalin do Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimeters o-Toluidine "grams" Formalin do Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimetersa-naphthylamine -grams Formalin do Conc. HCl cubic centimeters Exmrts IV Acetaldehyde reaction products Dilute waste sulphite liquor cubic centimeters Aniline grams Acetalydehyde do H2504 (1:1) cubic centimeters" Dilute waste sulphite liquor cubic centimeters Aniline "grams" Acetaldehyde do H2804 (1:1) cubic centimeters Dilute waste sulphite liquor cubic centimeters Phenylenediamine grams Acetaldehyde do Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimeters" Para phenylenediamine grams Conc. HCl cubic centimeters Acetaldehyde gr Dilute waste'sulphite liquor ....-cubic centimeters..'. Para phenylenediamine --grams... Cone. HCl cubic centimeters Acetaldehvde "grams.

Dilute waste sulphite liquor -cubic centimeters" Tolidine ....grams Conc. H01"; ..cubic centimeters Acetaldehyde "grams- Dilute waste sulphite liquor -cubic centimetersa-naphthylamine grams Acetaldehyde ..-do-- Conc. H01 cubic centimeters..-

ExmLnV Furfural reaction products Dilute waste sulphite liquors ..-cubic centimeters-- m-Phenylenediamine "grams" Furfural do Conc. H01 -cubic centimeters Dilute waste sulphite liquor";

cubic centimeter m-Phenylenediamine "grams..- Furfural do-.... Conc. HCl ..cubic centimeters- Dilute waste sulphite liquor"--. cubic centimeter 2, 4 toluylenediamine grams Furfural do Conc. HCl "cubic. centimetersilute waste sulphite liquor cubic centimeters Benzidine g1'ar ns- Furfural do Conc. HCl cubic centimeters Dilute waste sulphite liquor cubic centimeters a naphthylamine grams Furfural do Cone. I-ICl ..cubic centimeters EXAMPLE Y1 Mixed aldehyde reaction products Dilute waste sulphite liquor cubic centimeters Aniline grams Acetaldehyde do Fm'malin (in H2804 (1:1) 'oubic centimeters Dilute waste sulphite liquor;

cubic centimeters" Aniline "grams" Formalin cubic centimeters Furfural cubic centimeters H2804 (1:1) cubic centimeters" Dilute waste sulphite. liquor cubic centimeters. o-Toluidine -grams Acetaldehyde -1 -do Formalin do H1804 (1:1) cubic centimeters Dilute waste sulphite liquor cubic centimeters" Para toluidine grams- Acetaldehyde "do"..-

Formalin ....do

Conc. -HC1 ..cubic centimeters" amine-aldehyde precipitate of improved (e) Dilute waste sulphite liquor 1000 cubic centimeters" 1000 21.8 Xylidine gra ms 24.7 20.0 Aoetaldehy'de 'i 'do 8.8 8.8 Formalin do 11.3 Conc. HCl. ..cubic centimeters 20.0 1 0 (j) Dilute waste sulphite liquor 1 213 i cubic centimeters 1000 2 9 m-Phenylenediamine grams 21.6 3' Cone. HCl cubic centimeters 20.0 Acetaldehyde grams 8.8 moo Formalin -do 15.0 28.6 Exmm VII 3': V Mized amine reaction products (a) Dilute waste sulphite liquor j cubic centimeters- 1000 "Aniline grams 18.6 Phenyl-b-naphthylamine do 21.9 Conc. I -ICl cubic centimeters 20.0 Formalin "grams. 22.5 1000' (b) Dilute waste sulphite 1iquor -5 cubic centimeters 1000 v Aniline grams 18.6 o-Toluidine do 21.4

Formalin do 30.0 1000 H2504 (1:1) "cubic centimeters 20.0

ExAurLnV'III 20,0 Mixed aldehydes and mixed amine reaction products 1000 (a) Dilute sulphite waste liquor 24.4 cubic.centimeters 1000 4 Aniline grams 18.6 2 o-Toluidine do 21.4 H2804 (1:1) cubic centimeters 20.0 1000 Acetaldehy'de grams 8.8 13.4 Formalin .'do 15.0 213 The present invention also includes theprocess and products resulting therefrom in which the spent sulphite liquor has been subjected to a 1000 chlorine gassing treatment pnior to precipitation. The precipitates obtained from the sulphite liq uor which have been subjected to the preliminary chlorine gas treatment have low ash values, p i. e. around 0.1 percent, compared with ash values of the precipitates obtained from the raw or untreated pulping liquor which range from about 4-5 percent. My investigations have .shown that the precipitates having a low ash 1000 value and obtained from chlorinated sulphite 27 9 liquor exhibit better moldability than do the the precipitates obtained from the ordinary untreated liquor. The following example will. serve for illustrative purposes:

EXAMPLE IX 1000 About 13 grams of chlorine gas are blown into 20 about 1000 c. c. of dilute spent or waste sulphite 15 liquor. The amine, aldehyde and. mineral acids 25 are then added and .the reaction carried out in 15 accordance with Examples I or II. A resinous precipitate with a low ash value 0 may also be obtained from sulphite liquor when the waste sulphite liquor is subjected to a preliminary treatment which includes the following steps: addition of milk of lime to the spent sulphite liquor, separation of the liquor from the precipitate formed on addition of the milk 1000 of lime, addition of sulfuric acid to the liquor 21.4 and separation of the liquor from the precipitate 8.8 formed on the addition of the acid. This liquor 11.3 substantially free from lime salts. yields an 20.0 molding precipitates and the mixture shaped under heat etc. provides a lubricating film which prevents .the plastic from sticking to the mold.

for making plastics, etc. Fillers such as wood filler are ordinarily mixed, with the powdered and "pressure of around 125-'160 C. and 2000-4000 lbs. per square inch for about 3-15 minutes. The plastics after cooling have a resin-like appearance and exhibit remarkable strength, toughness and shock resistance. I have found that the addition to the molding powders of a small amount of flux or plasticizer such as glycerol, cresoL'acetone, furfural, aniline, hexamethylenetetramine, anhydroformaldehyde aniline, and the like to increase fluidity to be desirable in practice. The addition oi hexamethylenetetramine has also been found to decrease corrosive action during molding. My investigations have also shown the addition to the molding mixture of a small amount of insoluble Soap suchas zinc steara'te aluminum palmitate,

I have discovered when hydrochloric acid e. g. crude muriatic acid, is used in place-oi sulphuric acid in the above examples, that the resulting resinous precipitates have a very low ash content. I have also discovered that improved molding compositions may be-prepared by em-.

.ploying dilute sulphite'liquor having dispersed therein a filler such as wood flour, groundwood, sulphite pulp etc. The formation and precipitation of the resinous precipitate in 'the prestncc of the .illling material givcs'an intimate mixture of resin and filler, resulting in molding powders ot superior molding properties.

In the preparation of the plastic material from both hard and soft wood-dilute'sulphite liquors, it is possible to obtain satisfactory results by varying the order of addition of the chemicals, the temperature. the concentration v and by the axidation, acidification, ,alkaliniza- 'tion or halogenization oi the spent liquors. In

addition, the precipitates may be modified by the addition of other inorganic and organic materials to the reaction liquor. The preferred procedures may be found by experimental tests. The process described above gives a substant ally' complete precipitation of the desired resinous composition, the" resulting precipitates being separable from the liquor, both of which are essential ih' a commercially practical process. I claim:

1. The process of precipitating resinous comev positions from spent sulphite liquor which comprises mixing a primaryaromatic amine and an,

aldehyde with dilutesulphite liquor in the presence ota strong acid.

2. The process of preparing a resinous precipitate adaptablefor use in molding powders, which comprises precipitating the resinous composition contained in sp nt acid minu -l u 'r'mlxinc a primary aromatic amine, an aldehyde and a mineral acid with dilute sulphite liquor, separatstrong acid.

sulphite liquor, aniline, formaldehyde I r 2,928,567 properties. The low ash precipitates obtained ing the precipitate thus formed from the liquor,

washing the precipitate and drying the precipltate.

3. Th process of precipitating resinous compositions from p nt sulphite liquor which comuprises mixing a primary aromatic amine and positions from spent sulphite liquor which com- 5. The process of precipitating resinous'comprises mixing toluidine. and formaldehyde with dilute sulphite liquor in the presence of a strong acid.

6. The process of precipitating resinous com positions from spent sulphite liquor which comprises mixing aniline and formaldehyde. with dilute sulphiteliquor in the presence of sulphuric acid.

"I. The process of precipitating resinous compositions from spent sulphite liquor which comprises mixing o-toluidine and formaldehyde with dilute sulphite liquor in the presence of hydrochloric acid. v 8. A resinous precipitate of the type described comprising the reaction product of dilute spent acid sulphite liquor, is primary aromatic amine, an aldehyde and 'a'mineral acid.

9. A resinous precipitate-of the type described comprising the reaction product of dilute spent sulphite liquor, a primary aromatic amine, formq aldehyde and a strong acid.

10. A resinous precipitate of the type described comprising the reaction product of dilute spent sulphite liquor, aniline, formaldehyde and a 11. A resinous precipitate of thetype described comprising the reaction product of dilute spent sulphite liquor, toluidine, formaldehyde and a strong acid.

12. A resinous precipitate of the type described comprising the reaction product of" dilute spent and sulfuric acid.

13. A resinous precipitate of the type descri comprising the reaction product of dilute spent;

sulphite liquor, o-toluidine, formaldehyde and a mineral acid. 1

14. A molding powder containing a low ash value resinous precipitate of the type described comprising a primary aromatic amine-aldehydemineral acid-dilute spent sulphite liquor reaction product, the ash value of said resinous precipitate being about 0.1 per cent.

15. A plastic comprising a reaction product, of

-' a primary aromatic amine, an aldehyde and dilute resinous precipl 

